Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen

Definitions

• R and R represent hydrogen, a hydrocarbon radical or a halogen atom
• R represents hydrogen or a hydrocarbon radical
• X represents the residue of an aromatic or saturated aliphatic dicarboxylic acid
• hydrocarbon radical includes alkyl, cycloalkyl, aryl, aralkyl and alkaryl radicals.
• radicals which may be represented by R and R include hydrogen, methyl, ethyl, propyl, isopropyl, octyl, phenyl and chlorine.
• the compounds of the present invention which are particularly useful are those in which R and R represent hydrogen or lower alkyl in particular methyl.
• radicals which may be represented by R include hydrogen, methyl, ethyl, n-propyl, isopropyl, nbutyl, sec-butyl, t-bntyl, isobutyl, pentyl, hexyl, dodecyl, cetyl, cyclohexyl, benzyl and phenyl.
• radical X which is the residue of an aromatic or saturated aliphatic dicarboxylic acid
• examples of the radical X which is the residue of an aromatic or saturated aliphatic dicarboxylic acid include the residues of oxalic, adipic, sebacic, succinic, pimelic, suberic, azelaic, phthalic, isophthalic and terephthalic acids.
• the residue X represents the valency bond joining the two carboxylic acid residues, in all other acids X represents the organic radical to which the carboxylic acid radicals are attached.
• the polymerisable bis-amides of the present invention are substituted bis-amides of the aromatic or saturated aliphatic dicarboxylic acids X(COOI-I) the substituent being the 3,4-dihydro-ZH-pyran-Z-methyl radical or a similar radical in which the pyran ring is substituted in the 2- and/or 5-positions.
• R represents a substituent other than hydrogen the bis-amides are completely substituted on the nitrogen atoms.
• polymerisable bis-amides of the present invention examples include:
• the polymerisable bis-amides of the present invention may be manufactured by reacting a 2-aminoethyl-3,4-dihydro-2H-pyran (optionally ring substituted in the 2- and/ or S-positions) or a N-monosubstituted derivative thereof with an aromatic or saturated aliphatic dicarboxylic acid or an amide-forming derivative thereof such as an acid halide or ester.
• R R and R are as hereinbefore defined with an aromatic or saturated aliphatic dicarboxylic acid or an amide forming derivative thereof.
• Examples of 2-aminomethyl-3,4-dihydro-2H-pyran derivatives of the general Formula II which may be used as starting materials in the present process include:
• 2-arnino methyl-3,4-dihydro-2H- pyran Z-aminomethyl-Z,S-dimethyl-3,4-dihydro2H-pyran, Z-aminomethyl-Z,S-diethyl-3,4-dihydro-2H-pyran, Z-N-methylaminomethyl-Z,S-dimethyl-3,-4-dihydro-2H- Py 2-N-methylaminomethyl-3,4-dihydro-2H-pyran, Z-N-phenylaminomethyl-3,4-dihydro-2H-pyran, Z-N-cyclohexylaminomethyl-3,4-dihydro-2H-pyran, 2-N-benzylaminomethyl-3,4dihydro-2Hpyran, 2-aminomethyl-2,5-dichloro-S,4-dihydro-2JH-pyran.
• aromatic or saturated aliphatic dicarboxylic acids which can be used in the present process there may be mentioned oxalic acid, adipic acid, sebacic acid, succinic acid, pimelic acid, suberic acid, azelaic acid, phthalic acid, isophthalic acid, and terephthalic acid.
• esters and acid halides examples of amide forming derivatives of such dicarboxylic acids which can be used there may be mentioned esters and acid halides.
• esters of such dicarboxylic acids which may be used include the methyl, ethyl, propyl and butyl esters.
• acid halides of such carboxylic acids which can be used include the acid chlorides and acid bromides.
• reaction leading to the formation of the polymerisable bis-amides of the present invention is carried out using known techniques, for example when using the ester or acid chloride of a dicarboxylic acid an acid binding agent is normally employed.
• the polymerisable bis-amides of the present invention contain two polymerisable vinyl ether groupings and may be used in the manufacture of polymeric materials either as one of the main polymer forming components or as cross-linking agents.
• the polymerisable bis-amides may be polymerised to give homopolymers by the action of catalysts known to polymerise vinyl ethers, they may also be copolymerised with other vinyl ethers using the same type of catalyst.
• Suitable catalysts include both acidic and nonacidic catalysts, particularly acidic catalysts.
• suitable catalysts include strong proton-donating acids such as hydrochloric acid, p-toluene sulphonic acid and Lewis acids such as trimethoxy boroxine and boron trifluoride conveniently employed as the etherate, BF (C H O.
• Suitable acid catalysts include ferric chloride, stannic chloride, phosphorus pentachloride, phosphoric acid, boron trifiuoride dihydrate, hydrogen fluoride, antimony pentafiuoride, hexafluorophosphoric acid, lead fluoborate, antimony fluorborate, sulphuric acid and silico-tungstic acid, and non-acid catalysts such as iodine and iodine perchlorate, iodine acetate, iodine triphosphate and iodine triacetate and triphenyl methyl derivatives of anions having a low ester forming tendency, for example triphenylmethyl perchlorate, hexachloroantimonate, chloromercurate, chlorozincate and chloroaluminate.
• Examples of other vinyl ethers which may be used in the formation of copolymers with the polymerisable bisamides of the present invention include methyl vinyl ether, ethyl vinyl ether, hexyl vinyl ether, divinyl ether, diisopropenyl ether, diethylene glycol divinyl ether, butane diol divinyl ether and vinyl ethers containing one or more dihydropyran nucleii such as 3,4-dihydro-2H-pyran, 3,4-dihydro-2H-pyran-2-methy1 (3,4-dihydro ZH-pyran- Z-carboxylate) also known as acrolein tetramer, bis-esters of 2-hydroxymethyl-3,4-dihydro-2H-pyran with di-basic acids such as succinic acid, adipic acid and phthalic acid, and aldol-type condensation products derived from acrolein dimer.
• a foam-forming gas may be generated by methods know in the art, for example by incorporating a low boiling inert liquid such as a halogenated aliphatic hydrocarbon into the polymerisation mixture; the heat of polymerisation volatilising the inert liquid to form small bubbles in the polymerised mass.
• a low boiling inert liquid such as a halogenated aliphatic hydrocarbon
• Suitable halogenated hydrocarbons include trichloromonofluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, dibromodifluoromethane, dichlorohexaflurocyclobutane, methylene chloride, chloroform, trichloroethylene, carbon tetrachloride and perchloroethylene.
• a surfactant such as is used in the manufacture of foamed polyurethanes, for example a silicon surfactant such as siloxane-oxyalkylene copolymer for example of the type described in British Patent No. 892,136.
• the manufacture of homopolymers and copolymers from the polymerisable bis-amides of the present invention may be carried out by methods well known in the art for vinyl ether polymerisation.
• polyreactive materials reactive with vinyl ethers such as polyhydric alcohols, polyhydric phenols, dicarboxylic acids and epoxy compounds may also be incorporated in the polymerisation mixture in particular when manufacturing copolymers from the substituted amides of the present invention.
• the polymerisable bis-amides of the present invention may also be reactedwith water to form the 6-hydroxy derivatives of the general formula
• the 6-hydroxy derivatives of the above general formula may also exist in the tautomeric hydroxy aldehyde form.
• 6-hydroxy derivatives in either tautomeric form may also be used as polymer forming intermediates by reacting them with compounds containing active hydrogen atoms for example amines and active methylene compounds.
• Foamed polymers or copolymers made from the polymerisable bis-amides of the present invention may be used for insulation or as constructional materials.
• Homopolymers and copolymers produced from the polymerisable bis-amides of the present invention are also useful as surface coatings, textile finishes and in non-woven textile materials.
• agents such as are normally incorporated in the manufacture of polymeric materials, for example, plasticisers, pigments, colouring materials and fire retardants.
• EXAMPLE 2 Preparation of a foamed copolymer from the product of Example 1 10 parts acrolein tetramer, 2.5 parts N,N'-bis(3,4-dihydro-2H-pyran-2-methyl)phathalamide, 0.18 part of a siloxane oxyalkylene copolymer, and 4.5 parts trichloromonofiuoromethane are mixed with stirring and there is then added to the mixture 1.5 parts of a 10% solution of boron trifluoride etherate in polypropylene glycol of molecular weight 425. The mixture is then allowed to foam and gives a light brown cellular polymeric material.
• EXAMPLE 3 Preparation of N,N'-bis(3,4-dihydro-2H-pyran-2-methyl) adipamide
• EXAMPLE 4 Preparation of a foamed copolymer from the product of Example 3 15 parts acrolein tetramer, 2.5 parts N,N-bis(3,4-dihydro-2H-pyran-2-methyl)adipamide, 0.13 part of a siloxane oxyalkylene copolymer, and 2.1 parts trichloromonofiuoromethane are mixed with stirring and there is added 2.2 parts of a solution of borontrifluoride etherate in polypropylene glycol of molecular weight 425. The mixture is allowed to foam to a light brown cellular polymeric structure.
• EXAMPLE 6 Preparation of a foamed copolymer from the product of Example 5 10 parts acrolein tetramer, 2 parts N, N-bis(3,4-dihydro-2H-pyran-2-methyl)oxamide, and 1.2 parts diphenylol propane are warmed to give a clear solution. The mixture is cooled and there is added, with stirring, 0.12 part of a siloxane oxyalylene copolymer and 6 parts trichloromonofluoromethane followed by 1.5 parts of a 10% solution of boron trifluoride etherate in polypropylene glycol of molecular weight 425. The mixture is allowed to foam to a slightly off white cellular polymeric structure.
• EXAMPLE 9 Preparation of a foamed copolymer from the product of Example 8 10 parts acrolein tetramer, 2 parts N,N-bis(2,5-dimeth- 6 yl-3,4-dihydro-ZH-pyran-Z-methyl)oxamide, and 2 parts diphenylol propane are warmed to give a clear solution. The mixture is cooled and is stirred and there is added 0.12 part of a siloxane oxyalkylene copolymer, and 3.5 parts trichlorofluoromethane followed by 1.2 parts of a 10% solution of boron trifiuoride etherate in polypropylene glycol ofmolecular weight 425. The mixture is allowed to foam to a light brown cellular structured poly mer.
• R and R are members selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, and chlorine; R is a member selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, cyclohexyl, benzyl and phenyl; and X is the residue of a dicarboxylic acid selected from the group consisting of the oxalic acid, saturated aliphatic dicarboxylic acid con taining up to 8 carbon atoms in the carbon chain, and benzene dicarboxylic acids.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)

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Citations (1)

• 1964
  • 1964-10-30 GB GB44350/64A patent/GB1071816A/en not_active Expired
• 1965
  • 1965-10-21 US US500356A patent/US3431283A/en not_active Expired - Lifetime
  • 1965-10-28 NL NL6513970A patent/NL6513970A/xx unknown
  • 1965-10-28 DE DE19651493889 patent/DE1493889B2/de active Pending
  • 1965-10-28 BE BE671583D patent/BE671583A/xx unknown
  • 1965-10-29 FR FR36800A patent/FR1454679A/fr not_active Expired

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